Production improvement for substituted triazines

ABSTRACT

In the manufacture of the dyestuff intermediates of U.K. Pat. specification No. 914 932 by condensing 1 mole of an alkylene diamine and 1 mole of a N-(2,4-dihalogeno-s-triazin-6-yl) sulphoaniline or sulphonaphthylamine, products of higher purity are obtained by adding a neutral solution of the latter to an aqueous solution of a mineral acid salt of an alkylene diamine, the minimum amount of the diamine being 1. 2 molecular proportions of the 1,3,5,-triazine derivative, and the amount of mineral acid present being at least 1.9 molecular proportions, based on the alkylene diamine, and simultaneously adding an alkali to maintain the pH of the reaction mixture in the region of 6.5-7. A reaction temperature of 30* C. to 35* C is preferred. Alternatively, instead of adding alkali, 1-2moles of an alkali metal bicarbonate are added to the mineral acid solution of the alkylene diamine before starting to add the s-triazine compound. U.K. Pat. specification No. 914,932 describes and claims 2halogen-1,3,5-triazine derivatives which contain in the 4position of the triazine nucleus the residue of an alkylene diamine containing two primary or two secondary amino groups, and which contain in the 6- position the residue of a sulphophenylor sulphonaphthyl- amine bound through its amino group to the carbon atom of the triazine ring, and a process for manufacture of these derivatives by reacting an alkylene diamine containing two primary or two secondary amino groups in an aqueous medium with a water-soluble 2,4-dihalogeno- 1,3,5- triazine derivative which contains in the 6-position a sulphophenylamino or sulphonaphthylamino group. The specification states that to obtain substantially only an alkylene diamine derivative having a single monohalogen triazine group, it is advantageous to use approximately equimolecular proportions of the diamine and the dihalogen triazine derivative and to add the diamine to an approximately neutral solution of the dihalogen triazine derivative. It has not been found, however, that even purer monocondensation products can be obtained by a procedure differing from this stated preference. Accordingly the present invention provides an improved process for the compounds of specification No.914,932 which comprises adding a substantially neutral aqueous solution of a watersoluble 2,4-dihalogeno-1,3,5-triazine derivative which contains in the 6-position a sulphophenylamino or sulphonaphthylamino group, to an aqueous solution of a mineral acid salt of an alkylene diamine, the minimum amount of the diamine being 1. 2 molecular proportions of the 1,3,5-triazine derivative, and the amount of mineral acid present being at least 1.9 molecular proportions, based on the alkylene diamine, and simultaneously adding an alkali to maintain the pH of the reaction mixture in the region of 6.5-7. A reaction temperature of 30* to 35* C is preferred. In a modification of this process it has also been found that a similar excellent result can be obtained if an amount of an alkali metal bicarbonate, especially sodium bicarbonate, equivalent to one to two moles, preferably 1.5 moles, of the triazine derivative is added to the mineral acid solution of the alkylene diamine before starting to add the 1,3,5-triazine derivative. In this case, it is no longer necessary tO add alkali during addition of the 1,3,5-triazine derivative. The invention is illustrated but not limited by the following Examples in which parts are by weight:

United States Patent Baker et al.

[54] PRODUCTION IMPROVEMENT FOR SUBSTITUTED TRIAZINES [72] Inventors:Ronald Baker; Thomas 'Kirkly Storer, both of Blackley, Manchester,England [73] Assignee: Imperial Chemical Industries Limited, London,England [22] Filed: Aug. 24, 1970 [21] Appl. No.: 66,579

[30 I Foreign Application Priority Data Nov. 20, 1969 Great Britain..56,850/69 52 us. ca ..260/249.8 [51] Int; Cl. ..C07d 55/46 v [58].;Field of Search ..260/249.8

[56] References Cited UNITED STATES PATENTS 2,393,755 1/1946 DAlelio.,....260/249.8 X 3,235,359 2/1966 Acker ..260/249.8 X

Primary Examiner-John M. Ford Attorney-Cushman, Darby & Cushman 51 Sept.12,1972

[5 7] ABSTRACT In the manufacture of the dyestuff intermediates of U.I(.Pat. specification No. 914 932 by condensing 1 mole of an alkylenediarnine and 1 mole of a N-(2,4- dihalogeno-s-triazin-fi-yl)sulphoaniline or sulphonaphthylamine, products of higher purity areobtained by adding a neutral solution of the latter to an aqueoussolution of a mineral acid salt of an alkylene diarnine, the minimumamount of the diarnine being 1. 2 molecular proportions of thel,3,5,-triazine derivative, and the amount of mineral acid present beingat least 1.9 molecular proportions, based on the alkylene diarnine, andsimultaneously adding an alkali to maintain the pH of the reactionmixture in the region of 6.5-7. A reaction temperature of 30 C. to 35 Cis preferred.

Alternatively, instead of adding alkali, l-2moles of an alkali metalbicarbonate are added to the mineral acid solution of the alkylenediarnine before starting to add the s-triazine compound.

5 Claims, No Drawings PRODUCTION IMPROVEMENT FOR SUBSTITUTED TRIAZINESU.l(. Pat. specification No. 914,932 describes and claims 2halogen-l,3,5-tr iazine derivatives which contain in the 4-position ofthe triazine nucleus the residue of an alkylene diamine containing twoprimary or two secondary amino groups, and which contain in the 6position the residue. of a sulphophenylor s ulphonaphthylamine boundthrough its amino group to thecarbon atom of the triazine ring, and aprocess for manufacture of these derivatives by reacting an alkylenediamine containing two primary or two secondary amino groups in-anaqueous medium with a water- Accordingly the present invention providesan imliberated and the pH remains constant without the further additionof sodium carbonate. The solution is freed from excess cyanuric chlorideby filtration and retained for reaction with ethylene diamine. Preparatory to the second stage of the condensation 3.6 partsof ethylene diamineare dissolved in 2,000 parts of water and the solution is adjusted to pH7.0 by the addition of 75.5 partsof hydrochloric acid 8.6. 1.18; 63parts of sodium bicarbonate are added to the mixture to give a resultingpH of 6.5. The temperature is raised to 30-35 C and the solution of2,4-dichloro-6-(2,5- disulphophenylamino)-s-triazine prepared asdescribed is added during l-2 hours. The mixture is stirred at 30-35 Cfor hours and is then allowed to cool to C. The product is precipitatedby the addition of 20 percent of sodium chloride, isolated byfiltration, and

- washed with 750 parts of 20 percent sodium chloride.

solution. The aqueous paste so obtained contains 2-N EXAMPLE 2Sixtyparts of ethylene diamine are dissolved in 2,000

. parts of water and the solution is adjusted to pH 7.0 by

proved process for the compounds of specification No.914,932 whichcomprises adding a substantially neutral aqueous solution of awater-soluble 2,4- dihalogeno-l,3,5-triazine derivative which containsin the 6-position a sulphophenylamino or sulphonaphthylamino group, toan aqueous solution of a mineral acid salt of an alkylene diamine, theminimum amount of the diamine being 1; 2 molecular proportionsof thel,3,5-triazine derivative, and the amount of mineral acid present beingat least 1.9 molecular proportions, based on the alkylene diamine, andsimultaneously adding an alkali tomaintain the pH of the reactionmixture in the region of 6.5-7. A reaction temperature of to C ispreferred.

" In a modification of this process it has also been found that asimilar excellent result can be obtained if an amount of an alkali metalbicarbonate, especially sodium bicarbonate, equivalent to one totwo'moles, preferably 1.5 moles, of the triazine derivative is added tothe mineral acid solution of the alkylene diamine before starting to addthe 1,3,5-triazine derivative. in this case, it is no longer necessaryto add alkali during addition of the 1,3,5-triazine derivative.

. The invention is illustrated but not limited by the following Examplesin which parts are by weight:

EXAMPLE 1 126.5 parts of l-aminobenzene-2,5-disulphonic acid are stirredwith 175 parts of water and sufficient ION sodium hydroxide solution isadded to bring to pH 7.0.

complete when no further hydrochloric acid is the addition of 126 partsof hydrochloric acid 8.6. 1.18. 1,000 parts of sodium chloriderepresenting 20 percent w/v of the final solution are added and thetemperature of the mixture is raised to 30-35 C. The mixture is stirredanda solution of 2,4-dichloro-6-(2,5- disulphophenylamino)-s-triazineprepared from 126.5 parts of l-aminobenzene-2,S-disulphonic acid by themethod described in Example 1 is added during 3 hours, the pH of themixture being kept at 65-70 by the simultaneous addition of 2N sodiumcarbonate solution. Stirring is continued at 30-35 C until no furtheraddition of sodium carbonate is required to maintain the pH. The mixtureis then allowed to cool to 20 C andthe insoluble product is filtered offand washed with 750 parts of 20 percent sodium chloride solution, thecream colored aqueous paste so obtained contains disulphophenylamino)-striazine essentially free from the his condensation product.

EXAMPLE-3 86.5 parts of l-aminobenzene-3-sulphonic acid are stirred with200 parts of water and sufficient ION sodium hydroxide solution is addedto bring to pH 7.0. This solution is added dropwise to a stirred mixtureof 97 parts of cyanuric chloride, 225 parts of water, 575 parts of iceand 2 parts of Calsolene Oil HS. The hydrochloric acid formed in thereaction is neutralized by the simultaneous addition of 2N sodiumcarbonate solution at such a rate as to maintain the mixture at pH6.57.0, and the temperature is maintained at 0-5 C by the addition offurther ice. The condensation is complete when no further hydrochloricacid is liberated and the pH remains constant without the furtheraddition of sodium carbonate. The solution is freed from the excess ofcyanuric chloride by filtration. 36 parts ofethylene diamine aredissolved in 2000 parts of water and the solution is adjusted to pH 7.0by the addition of 75.5 parts of hydrochloric acid 8.6. 1.18; 63 partsof sodium bicarbonate are added to the mixture to give a2-N-B-aminoethylamino 4-chloro-6-( 2 ,5-

resulting pH of 6.5. The temperature is raised to 30- 35 C and the abovesolution of 2,4-dichloro-6-(3- sulphophenylamino)-s-triazine is addedduring 1-2 hours. The mixture is stirred at 30-35 C for hours and isthen allowed to cool to 20 C. The precipitation of the product iscompleted by the addition of sodium chloride and is isolated byfiltration. Essentially pure 2-N-B-aminoethylamino-4-chloro-6-(3-sulphophenylamino)-s-triazine isobtained in good yield.

Analogous compounds are obtained by replacing thel-aminobenzene-3-sulphonic acid in the above example by the equivalentquantity of l-aminobenzene-Z- sulphonic acid, l-aminobenzene-4-sulphonicacid, 1- amino-2-carboxybenzene-4-sulphonic acid, 1-amino-2-methylbenzene-4-sulphonic acid, or of 2- aminonaphthlene-4,8-disulphonicacid.

EXAMPLE 4' 126.5 parts of 1-aminobenzene-2,S-disulphonic acid arestirred with 175 parts of water and sufficient ION sodium hydroxidesolution is added to bring to pH 7.0.

This solution is added rapidly to a stirred mixture of 97' parts ofcyanuric chloride, 225 parts of water, 575 parts of ice and 2 parts ofCalsolene Oil HS. The hydrochloric acid formed in the reaction isneutralized by the dropwise addition of 2N sodium carbonate solution atsuch a rate as to maintain the mixture at pH 6.57.0. The temperature ismaintained at 35 C by the addition of further ice as required. Thecondensation is complete when no further hydrochloric acid is liberatedand the pH remains constant without the further addition of sodiumcarbonate. The solution is freed from excess cyanuric chloride byfiltration. 44.7 parts of 1:2-propylene diamine are dissolved in 2,000parts of water and the solution is adjusted to pH 7.0 by the addition of75.5 parts of hydrochloric acid S.G. 1.18; 63 parts of sodiumbicarbonate are added to the mixture to give a resulting pH of 6.5. Thetemperature is raised to 30-35 C and the above solution of 2,4-dichloro-6-(2,5-disulphophenylamino)-s-triazine is added duringl-2hours. The mixture is stirred at 3035 C for 5 hours and is thenallowed to cool to 20 C. The product is precipitated by the addition of20 percent of sodium chloride, isolated by filtration, and washed with20 percent sodium chloride solution. The product obtained is virtuallyfree from bis condensed material.

What we claim is:

1. An improved process for the manufacture of 2- halogen-l,3,5-triazinederivaties which contain in the 4-position of the triazine nucleus theresidue of an alkylene diamine containing two primary or two secondaryamino groups, and which contain in the 6- position the residue of asulphophenylor sulphonaphthylamine bound through its amino group to thecarbon atom of the triazine ring, which comprises adding a substantiallyneutral aqueous solution of a water-soluble 2,4-dihalogeno-1,3,5triazinederivative which contains in the 6-position a sulphophenylamino orsulphonaphthylamino group, to an aqueous solution of a mineral acid saltof an alkylene diamine, the minimum amount of the diamine being 1. 2molecular proportions of the 1,3,5-triazine derivative, 'and the amountof mineral acid present being at least 1.9 molecular proportions, basedon the alkylene diamine, and simultaneously adding an alkali to maintainthe pH of the reaction mixture in the region of 6.5- -7.

2. A process as claimed in claim 1 1n WlllCh the reaction is carried outat a temperature of 30-35 C.

3. A modification of the process claimed in claim 1 wherein, instead ofadding alkali, an amount of an alkali metal bicarbonate equivalent toone to two moles of the triazine derivative is added to the mineral acidsolution of the alkylene diamine before starting to add the triazinederivative.

4. A process as claimed in claim 3 wherein the amount of alkali metalbicarbonate is 1.5 moles, based on the triazine derivative.

5. A process as claimed in claim 3 wherein the alkali metal bicarbonateis sodium bicarbonate.

2. A process as claimed in claim 1 in which the reaction is carried outat a temperature of 30*-35* C.
 3. A modification of the process claimedin claim 1 wherein, instead of adding alkali, an amount of an alkalimetal bicarbonate equivalent to one to two moles of the triazinederivative is added to the mineral acid solution of the alkylene diaminebefore starting to add the triazine derivative.
 4. A process as claimedin claim 3 wherein the amount of alkali metal bicarbonate is 1.5 moles,based on the triazine derivative.
 5. A process as claimed in claim 3wherein the alkali metal bicarbonate is sodium bicarbonate.